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Carbanion-Mediated Heterocyclizations Regiospecific General Route to Dibenzo- [b e]phosphininones by Synthetic Anionic Equivalents of FriedelЦCrafts Reactions and Remote Fries Rearrangement.

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J = 7 . 6 Hz,2H), 7.73-7.80(m,4H),8.01 (I. J = 1 . 7 Hz), 10.04(s. 2H); (2)-5:
pale yellow oil; ' H N M R : 6 = 6.75 (s, 2H. J (H,H) = 12.2 Hz. J ("C.H) =
156.7 Hz from the I3C satellites), 7.34-7.47 (m, 2H). 7.71-7.75 (m, 2H). 9.90
(s. 2H).
T. Mukaiyama. T. Sato. J. Hanna. Cliem. Let!. 1973. 1041; J. E. McMurry.
Chem. Rev. 1989,89, 1513.
The synthesis of 8 has been described without spectral data 181. The spectral
LDAlTHF
data from our measurements: 'H NMR (270 MHz. CDCI,): 6 =7.34 (m. 6H).
7.38(dt.J=7.2.1.7 Hz).7.46-7.52(m.6H),7.72(dt,J=1.7.l.OHz)~"C
NMR (67.8 MHz, CDCI,): d = 88.59. 90.03, 123.11, 123.72. 128.41, 128.47,
131.31. 131. 70 (2C), 134.67; UV (cyclohexane): i,,, ( E ) = 268 (46800). 283
Ib
(66100). 301 nm (56200).
H. Zimmer. K. R. Hickey, R. J. Schumacher. Chimiu 1974. 28, 656; C.- J. F.
Du, H. Hart, J. Orx. Chem. 1987, 52, 4311.
FG
H. Meier. H. Petersen, H. Kolshorn. Chem. Ber. 1980, 113, 2398.
Review: H. Meier in Advances in Struin in Organic Chemistry. Vol.l (Ed.: B.
Halton), JAI Press, London, 1991. pp. 215-273.
Estimated by use of naphthalene (0= 0.23) as a standard; see: D. F. Eaton.
Pure Appl. Chem. 1988, 60. 1107
Crystal data for 1: C,,H,,, crystallized from toluene; M , = 400.5, monoclinic.
space group P2,/n (no. 14). a = 5.699(4), b =19.635(4). L' =19.260(2) A.
fl = 92.12(2)". V = 21 53(1) A', 2 = 4. pcAicd= 1.235 gem-', p = 0.70 cm1423 independent observed reflections with [F>3u(F), 3 ' 2 2 0 < 6 0 7 , refined
to R(Rw) = 0.041(0.042). Rigaku AFC5R difractometer with graphite
monochromated Mo,, radiation at 295 K. The structure was solved by direct
methods (SHELX-86) and refined with the TEXSAN crystallorgraphic software package of Molecular Structure Corporation. AII the non-hydrogen
atoms were refined anisotropically. Crystallographic data (excluding structure
factors) for the structure(s) reported in this paper have been deposited with the
Cambridge Crystallographic Data Centre as supplementary publication no.
CCDC-179-66. Copies of the data can be obtained free of charge on applicaScheme 1. LDA = lithium diisopropylamide, TMS = trimethylsilyl
tion to The Director, CCDC. 12 Union Road. Cambridge CB2 1EZ. UK (fax:
Int. code +(1223) 336-033; e-mail: teched(r, chemcrys cam.ac.uk)
Fable 1. Carbanionic route to dibenzo[b,e]phosphininones.PG = protecting group.
N. L. Allinger, A. Y Meyer, Telrahedron 1975. 1807.
M. Bauer, M. Nieger, F Vogtle, Chem. Ber 1992, 125, 2533.
Entry
Substrate
Equiv LDA
Product
Yield [%] [a]
(m.p. W l )
4
1
',
1
2.2
2
2.2
3
3.4
&
OOP
'h
X=NEt2;81
X = NiPr2; 98bl
X =OH; 75
2
(220-222)1CI
Carbanion-Mediated Heterocyclizations:
Regiospecific, General Route to Dibenzo[b,e]phosphininonesby Synthetic Anionic
Equivalents of Friedel- Crafts Reactions and
Remote Fries Rearrangement**
4
2.9
76
(167-167.5)
Matthew Gray, Brian J. Chapell, Nicholas J. Taylor,
and Victor Snieckus*
We report on the first carbanion-mediated synthesis of diverse
dibenzo[b,e]phosphininones 2 and 3 from carbamoyl and carbamoyloxy triarylphosphane oxides, 1a and 1b respectively
(Scheme l ) , which, conceptually, represent synthetic equivalents of anionic Friedel -Crafts and remote Fries rearrangements. This fundamental new chemistry of triarylphosphane
oxides, suggested by the Complex Induced Proximity Effect
(CIPE),"' is part of an emerging general class of lithiationinduced regiospecific heterocyclizations,'21which allows mild and
regioselective access to substituted, condensed, and heterocyclefused phosphininones (Table 1 ) . Moreover, this sparsely investigated class of P - h e t e r o ~ y c l e sof
, ~ significance
~~
to fundamental
'c
5
80
4.0
(278-279.5)
5
6
2.2
99
(160-161)
7
2.2
&go
PG = OMe; 78
(252-253)
8
[*] Prof. V. Snieckus, Dr. M. Gray, B. J. Chapell,[+' Dr. N. J. Taylor"]
Guelph-Waterloo Centre for Graduate Work in Chemistry
University of Waterloo. Waterloo, N2L 3G1, O N (Canada)
Fax: Int. +(519)746-5884
e-mail : snieckus@!buh.uwaterloo.ca
[ '1 X-ray crystallographic analyses.
[**I
0 VCH
Verlagsgesellschuft mbH, 0.69451 Weinheim, 1996
PG = TMS;411*1
(187- 187.5)
/
-
We are grateful to NSERC Canada, the NSERC/Monsanto Industrial Chair
Award. and the Province of Ontario URIF program (Grant No.2318101) for
support of our synthetic programs.
1558
2.5
3
[a] Yields are of chromatographed material. [b] With Liftmp) (tmp = 2,2,6,6-tetramethylpiperidin-1-yl), yield = 87%. [c] Published m.p. 220-222'C [6a], 222223 "C [7b]. 223 "C [7c]. [d] The product of remote carbamoyl migration. (2-diethylcarbamoylphenyl)(2-hydroxy-3-trimethylsilylphenyl)phenylphosphaneoxide, was
also obtained in ca. 50% yield.
3 1 5 . 0 0 i .25/0
0570-0833~96/3513-1S58
Angew. Chem. Int. Ed. Engl. 1996, 35, No. 13/14
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studies of phosphorus
turnstile geometry,[51and the
aromaticity of phosphacycles,[6] has previously been inaccessible, mainly due to limitations inherent in the classical FriedelCrafts techn01ogy.l~-'I Added interest stems from the current
popularity of atropisomeric diarylphosphane ligands (e.g. binap) in asymmetric synthesis and homogeneous catalysis.[']
Encouraged by documentation on the effective properties of
P(O)Ph, in directing metalation [Directed Metalation Group
(DMG) properties] ,[91 we subjected the carbamoyl triarylphosphane oxides 1 a (R = Et, iPr), prepared by CIP(O)Ph, treatment of the corresponding orfho-lithiated benzamide
(Table l),[lol to lithium diisopropylamide (LDA, 2.2 equiv/
THF/O "C) and observed their smooth cyclization to give the
parent dibenzo[h,e]phorphorinone 2 (Table I, entries 1 and 2).
The recent important observation by Mortier" suggested cyclization of the corresponding carboxylic acid, which, in the
event, led to the same product in somewhat lower yield (entry 3 ) .
In entry 4. the potential competition between three sites for
metalation and cyclization to form either phosphininone or two
types of fluorenone (arrows a, b, and c) is not observed, and
only a phosphininone is obtained. The structure was confirmed
by X-ray crystallographic
Double anionic cyclization of a dicarboxamide-substituted triaryl phosphane oxide
(entry 5) leads efficiently (47 % overall yield based on starting
benzamide) to 5H.9H-phosphinolino[3,2,1-de]-14-h5-acridophosphine-5,9.14-trione (5), a polycyclic system previously prepared by lengthy Friedel - Crafts approaches (overall yield
less than
Its X-ray crystal structure (Fig. 1) shows
'.'
U
LOAITHF
-20-c
Ph
6
7
Scheme 2.
when subjected to slightly modified cyclization conditions
(2.2 equiv LDA/THF/ - 20 "C), furnished the phosphepine 7
(ca. 50 % yield), a ring system with meager literature and potential antidepressant a ~ t i v i t y . ~ ~ ~ ]
To probe the potential involvement of CIPE"] in the anionic
Friedel-Crafts reaction, l a (R = Et) was subjected to LDA
(1.1 equiv; THF/O°C/40 min) to give a mixture of phosphininone 2 and starting material in 61 :39 ratio (by 'H N M R spectroscopy; respectively, 65 % and 27 % yields of isolated
product). Exposure of 1a (R = Et) to LDAiTMSCl (2.2 equiv/
2.5 equiv; T H F / -70 "C + 0 "C) under in situ conditions[l6]
provided 2 in 58% yield and only trace amounts of silylated
material. Thus cyclization appears to be fast with respect to
external electrophile trapping under the assumed thermodynamic conditions, but the relative contributions from amide
CIPE and P(0)Ph D M G effects require further investigation.
In summary, a general, convenient, and regiospecific entry
into benzo[b,e]phosphininones, including functionalized, polycyclic, and heterocyclic analogues, has been achieved by directed metalation tactics. The chemistry of this P-heteroatom
class," 71 previously inadequately explored because of synthetic
inaccessibility, may now be investigated, perhaps with emphasis
on development of new phosphane ligands for asymmetric synthesis!"]
Furthermore, this and related studiesr2]suggest that
carbanion-mediated cyclizations may provide fruitful new
methodology for the construction of other dibenzoannelated
six- and seven-membered ring heterocycles.
Experimental Procedure
Fig. 1. Structure of 5 in the crystal.
a puckered pentacyclic structure in contrast to the parent 2,
which exhibits only slight deviations from planarity. However,
the constraints of the pentacycle reduce pyramidality at phosphorus (sum of C-P-C bond angles, 319.9";cf. 316.8' in
2). [ l Z a ,b1 The scope of this new methodology is illustrated by the
preparation in quantitative yield of an indole-fused phosphininone (entry 6). a new ring system.['0.131
Tandem remote anionic Fries rearrangement[*"] and anionic
Friedel - Crafts reactions are observed on ortho-carbamoyloxy
triarylphosphane oxides (entries 7,8), leading to hitherto unknown P-phenyl functionalized phosphininones 3 (Scheme 1 ) .
The regiochemistry of the second deprotonation leading to intermediate 4 may be dictated by factors of higher electron density in the phenolic ring and OLi . . ' 0 = P coordination effects.
In analogy to observations from other heteroatom-bridged
biaryls,I2] the orrho-tolyl phosphane oxide 6 (Scheme 2),EL4]
Angeu Chrm Inl. Ed. Engl. 1996, 35, No. 13/14
6
2: N,N-Diisopropylamine (0.21 mL, 1.52 mmol) in dry T H F (12 mL) at temperatures below -7O'C under argon was treated with n-butyllithium (0.90 mL, 1.61 M
solution in hexanes, 1.45 mmol) by dropwise addition, and the mixture was stirred
at 0 ?C (20 min). (2-Diethylcarbamoylpheny1)diphenylphosphaneoxide (250 mg.
0.66 mmol) in THF (3.5 mL) was added dropwise to this solution at be < 2 "C by
cannula over 5 min, and the resulting brown suspension was stirred at 0'-C for
30 min. Saturated aqueous NH,CI was added, and the mixture extracted with ethyl
acetate, washed with brine, dried (MgSO,), and concentrated in vacuo. Purification
by column chromatography (97/3 CH,CI,/MeOH eluent) afforded 10-phenyl-9,lOdihydro-10-h5-acridophosphine-9,lO-dione
(163 mg, 81 YO):
colorless needles, m.p.
220-222°C (MeOH), (published m.p. 220-222°C. see Table 1). 1R (KBR. cm-'):
C : 3055, 1666, 1200; ' H N M R (250 MHz, CDCI,): 6 = 8.49-8.40 (m. 2H). 8.087.96 (m. 2H). 7.78-7.68 (m, 4H). 7.64-7.54 (m, 2H). 7.49-7.33 (m, 3H); 'IP
NMR (81 MHz, CDCI,. ext. ref. P(OMe), in C,D,). 6 = 4.0; MS (EI): ,n/z ( O h ) :
304 (44) [ M ' ) ; anal. calcd for C,,H,,O,P: C 75.00; H 4.31: P 10 18. Found: C
75.26: H 4.46; P 9 96.
Received. December 12, 1995
Revised version: March 18, 1996 [Z8639IE]
German version: AngeM.. Chem. 1996, 108, 1609-1611
Keywords: Friedel - Crafts reactions . Fries rearrangements
heterocycles - rearrangements - phosphorus compounds
.
[1] P. Beak. A. I. Meyers, Acc. Chem. Rex 1986, 19, 356-363.
[2] Cyclizations of a ) orfho-carbamoyl diaryl sulfone: F. Beaulieu, V. Snieckus,
J Org. Chem. 1994. 59, 6508-6509: b) corresponding diaryl ethers: 0. B.
Familoni. I.Ionica, V. Snieckus. Terruhedron Lett.. submitted; c) corresponding diarylamines: J. A. Glanzer, M. Gray, S. MacNeil, V. Snieckus. unpublished results.
[3] L. D. Quin, The Hererocyclic Chemistry of Phosphorus; S ~ s t c m bused
s
on the
Phosphorus- Curbon Bond, Wiley, New York, 1981.
PI C. H. Chen, J. J. Doney. J. L. Fox, H. R. Luss, .lOrg. Chon. 1985,50. 29142917.
VCH Verlugsgesellschuft mbH, 0-69451 Weinheim, 1996
0570-0833/96/3513-1559 S15.00.k ,2510
1559
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[5] D. Hellwinkel. A. Wiel, G. Sattler, B. Nuber, Angen. Chem. 1990, 102, 677680; Angew. Chem. Int. Ed. Engl1990, 29,689-692.
(61 a) C. Jongsma, R. Lourens, F. Bickelhaupt, Tetrahedron 1976, 32, 121-124;
b) C. Jongsma, H. Vermeer, F. Bickelhaupt, W. Schafer, A. Schweig, b i d . 1975,
31,2931 -2935; c) H. S. Kasmai. J. F. Femia, L. L. Healy, M. R. Lauria, M. E.
Lansdown. J. Org. Chem. 1987,52. 5461 -5466.
I
Org. Chem. 1964. 29, 2382171 a) G. 0 . Doak, L. D. Freedman, J. B. Levy, .
2385; b) Y Segall, I. Granoth, A. Kalir, J Chem. Soc. Chem. Commun. 1974,
501 -502; c) K. A. Petrov, V. A. Chauzov, N. Yu. Mal'kevich, Zh. Obshch.
Khim. 1977, 47. 2516-2522; J. Gen Chem. USSR 1977, 2299-2304 [Chem.
Abstr. 1978, XX, 89768~1.
[8] R. Noyori, Asymmetric Catalysis in Organic Synthesis, Wiley. New York. 1994.
[9] a) R. Schmid, J. Foricher, M. Cereghetti, P. Schonholzer, Helv. Chim. Acta
1991, 74, 370-389; b) J. M. Brown, S. Woodward, J Org. Chem. 1991, 55,
6803-6809; C)N. W. Alcock, J. M. Brown, M. Pearson, S. Woodward. Tetrahedron Asymmetry 1991,3.17-20; d) B. Schaub, J. Titus, M. Schlosser, Tetrahedron Leu. 1984, 37, 4097-4100. Other P-containing DMGs: e) D. C. Craig,
N. K. Roberts, J. L. Tanswell, Aust.J. Chem. 1990, 43, 1487-1496
(DMG = P(S)(NMe,),); f) M. Yoshifuji, T. Ishizuka, Y. J. Choi. N. Inamoto,
Tetrahedron Lett. 1984,25,553-556 (DMG = P(S)Ph(NR,)); g) L. Dashan, S.
Trippett, ihid. 1983, 24. 2039-2040 (DMG = P(O)(NMe,),); h) C. G. Stuckwisch, J Org. Chem. 1976,41, 1173-1176 (DMG = P(NPh)Ph,).
[lo] Reactions wereconducted indilutesolutions [12- 16 mL THF permmolexcept
entry4(30 mLTHF permmol)]. Yields 59-92%. Standard conditions: entries
1, 7, and 8 (2, 3): a) 1.1-1.15 equiv sBuLi/TMEDA (inverse addition), THF,
40-90min. < -70°C; b) 1.2-1.25equiv Ph,POCI, 20-60min. < -70°C;
c ) sat. aq. NH,CI; entry 2 (2). b) 1.2equiv Ph,POCI,< -70°C +room temperature (RT); entry 3: prepared according to a known procedure [9d]: entry
4: 2.5 equiv .sBuLi/TMEDA, 3.0 equiv Ph,POCI; entry 5 (5): b) 0.6 equiv PhPOCI,, 20min, < -7O'C; entry 6. normal addition and b) 1.25equiv
Ph,POCI, < -70 "C RT.
Ill] a) J. Mortier, J. Moyroud, B. Bennetau, P. A. Cdin. J Org. Chem. 1994, 59,
4042-4044; b) B. Bennetau, J. Mortier, J. Moyroud, J.-L. Guesnet, J Chem.
Sac. Perkin Trans. 11995, 1265-1271.
[12] a) Crystallographic data (excluding structure factors) for the structures reported in this paper have been deposited with the Cambridge Crystallographic
Data Centre as supplementary publication no. CCDC-179-64. Copies of the
data can be obtained free of charge on application to The Director, CCDC, 12
Union Road, Cambridge CB2 IEZ, UK (fax: Int. code +(1223) 336-033;
e-mail: teched@chemcrys.cam.ac.uk). b) Crystal data for entry 5 :
C,,H, ,O,P.CH,OH, M , = 363.33, colorless needle prism fragment of dimensions (mm) 0.34{110) x0.84{001), monoclinic, D/a, u =14.204(1). h =
ll.OlS(1). c = 21.617(2) A, /s' = 99.46(1)", V = 3336.0(5)
2 = 8. F(OO0) =
1504,~
= 1 . 4 4 3 g ~ m - ~ , 4 " s 2 8 s 5 0 , w s c a n m o d eT, = 200K.largestdiffer. were collected on a Siemens P4 difence peak/hole 0.31/ - 0.28 e k 3Data
fractometer with Mo,, radiation (2 = 0.71073 A). Of 3074 reflections measured, 2939 were independent. The structure was solved with direct methods
(SHELXTL IRIS) and refined by full-matrix least-squares on F(296 parameters), resulting in final R, wR, and GoF values of 0.0308, 0.0352, and 3.03
respectively (for 2476 data with F > 6.0o(F)). Absorption correction was faceindexed numerical(p(Mo,,) = 1.90 cm- min./max. transmission 0.9275/
0.9502). Hydrogen atoms were solved according to a riding model with refined
isotropic temperature factors U.
(131 The starting material was prepared by directed metalation: X. Wdng, PhD
Thesis, University of Waterloo, 1992.
[14] Prepared by directed ortho-metalation with (0-Tol)P(Ph)CI [17a] as electrophile, with subsequent oxidation of the crude phoshane (H,O,).
[15] Y. Segall, E. Shirin. I. Granoth, Phosphorus Sul/iur Relar. Elrm. 1980, 8, 243254.
[16] a) T. D. Krizan. J. C. Martin, J. Am. Chem. SOC.1983,105,6155-6157, b) E. J.
Corey, A. W. Gross, Teiruhedron Lett. 1984, 25, 495-498.
[17] Simple transformations, for example Grignard and alkyllithium additions and
reduction to phosphanes have been reported. See refs. [6a, 7b-c] and a) Y
Segall, R. Alkabets, 1. Granoth, J Chem. Res. Swap. 1977,310-31 1 ;J Chem.
Res. Miniprint 1977, 3541 -3565; b) I . Granoth. Y. Segall. H. Leader, J. Chem.
Sac. Perkin Trans. 1 1978, 465-468; c) K.-C. Chen, S. E. Ealick. D. van der
Helm, J Barycki, K. D. Berlin, J Org. Chem. 1977.42, 1170-1177.
[18] H. Brunner, Top. Stereochem. 1988, p. 129.
The First Synthesis of Enantiopure (-)- and
( + )-Isoterrein from Optically Inactive mesoTartaric Acid**
Marian Mikolajczyk,* Maciej Mikina, Michal
W. Wieczorek, and Jaroslaw Blaszczyk
Dedicated to Professor Leopold Homer
on the occasion of his 85th birthday
(+)-Terrein (+)-1, a metabolite of the mold Aspergillus terreus, was first isolated by Raistrick and Smith in 1935.['] Twenty
years later its correct structure was established independently by
Grove['] and by Barton and Miller,[31who also determined the
configuration of the trans-diol moiety by conversion of (+)-1
into a derivative of (+)-tartaric acid. Although the structure of
terrein 1 is simple, its synthesis is not trivial because of its sensitivity to acids and bases. Therefore, only after a lapse of twenty
years were three synthetic approaches to racemic terrein 1 rep ~ r t e d . [ ~In
- ~addition
]
to the synthesis of 1, Barton and Hulshofl5]also described the preparation of racemic isoterrein 2, the
more stable isomer of 1, in which the hydroxyl groups are cis
oriented.
--f
(+) - terrein (+) - 1
0
(-)
- terrein
(-)
-1
0
A3,
',
Only recently, two research groups succeeded in synthesizing
optically active terrein. Kolb and Hoffmann"] prepared first
racemic terrein 1 by ring contraction of 6-alkoxy-2,3-dihydro6H-pyran-3-one. Then after resolving racemic precursors of 1,
they completed the total synthesis of natural (+)- and unnatural
( -)-terrein. Altenbach and Holzapfel[8]devised an elegant and
short synthesis of ( + ) - I from L-( +)-tartaric acid utilizing the
chemistry of bis(fl-oxophosphonates). The synthesis and reactivity of this new class of phosphonates was independently and
intensively investigated in our laboratory.[g1As a result of our
studies we report here the first synthesis of both enantiopure
forms of isoterrein, (-)-2 and ( +)-2.['01
In developing the strategy for the synthesis of both enantiomers of isoterrein we noted that both (+)-terrein and (+)tartaric acid used in the synthesis of (+)-terrein have the same
configuration at the trans-diol moiety. Since isoterrein has a
cis-diol unit, meso-tartaric acid would appear to be a suitable
starting material; however, it is optically inactive. Therefore, it
was necessary to first seek a way to convert meso-tartaric acid
into an optically active derivative such that the configurational
[*] Prof. Dr. M. Mikolajczyk, M. Mikina
Centre of Molecular and Macromolecular Studies
Polish Academy of Sciences
Sienkiewicza 112, PL-90-363 Lodi (Poland)
Fax: Int. code +(42)847126
[**I
1560
Q VCH Verlagsgesellschaft mbH, 0-69451 Wemheim, 1996
Dr. M. W. Wieczorek, Dr. J. Btaszczyk
Institute of Technical Biochemistry, Technical University of t b d i
Stefanowskiego 4/10. PL-90.924 Lodl (Poland)
Financial support by the State Committee of Scientific Research (Grant No.
3/T09A/08408) and by the Foundation of Polish Science(for J. B.) is gratefully
acknowledged.
0570-0833/96/3S13-1540$15.00+ .25/0
Angew. Chem. Inr. Ed. Engl. 1996, 35, No. 13/14
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